1. Field of the Invention
The present invention relates to compositions usefule as thickening agents for aqueous sytems. More particularly, it relates to compositions comprising smectite clays and cationic polymers.
2. Description of the Prior Art
U.S. Pat. No. 4,157,388 (Christiansen issued Jun. 5, 1979) describes a variety of cationic polymers. A typical product according to that patent is of the formula: ##STR1## wherein n is at least one.
The products are stated to be of use as conditioning agents in shampoos, as anti-static and humectants for fibrous textile products and anti-dusting agents for powders.
In commonly assigned copending application Ser. No. 758,483 filed on Jul. 24, 1985 which is a continuation-in-part of application Ser. No. 458,197 filed on Aug. 15, 1983, there are described products of the general Formula: ##STR2## wherei R.sub.1, R.sub.2, R.sub.3, and R.sub.4 may be the same or different and select the group consisting of hydrogen, methyl, ethyl, propyl, --CH.sub.2 CH20H, --CH.sub.2 CH(OH)CH.sub.3 and --CH.sub.2 CH.sub.2 (OCH.sub.2 CH.sub.2)pOH wherein p is an integer from 0 to 6 with the proviso that not all of R.sub.1, R.sub.2, R.sub.3 and R.sub.4 are hydrogen; x and y are the same or different and are an integer from 1 to 6;
n is a value such that the number average molecular weight of the product is in excess of 20,0000; PA0 m is an integer from 0 to 34, for example, 3-10, typically 4-7; PA0 D is a halide ion; PA0 L is a linkage derived from a dihalide after removal of the halogen atoms, x and y are integers ranging from 1-100, PA0 and w is 0 or 1
X is halogen;
Z is halogen or amino-diamido ammonium residue; and
A is the residue of a dihalide.
U.S. Pat. No. 4,719,282 (Nadolsky et al) describes certain block copolymers of the formula: ##STR3## wherein: R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.5, R.sub.6, R.sub.7, and R.sub.8 are the same or different and are generally selected from the group consisting of C.sub.1 -C.sub.3 alkyl, C.sub.1 -C.sub.3 hydroxyalkyl, or hydroxy polyoxy-alkylene;
m is an integer from 0 to 34,
p, q, r and s are the same or different and are integers from 1 to 6,
and Q is (BL)y where the bonds between L and A or B are carbon-nitrogen bonds formed by quaternization of the tertiary amine functions of A and B by the organic dihalides from which L is derived
which are obtained by first forming a block of units by reacting a monomer of the formula II ##STR4## wherein each of R.sub.5, R.sub.6, R.sub.7, and R.sub.8 are the same or different and is selected from the group consisting of C.sub.1-3 alkyl, C.sub.1-3 hydroxy alkyl and hydroxy polyoxyalkylene,
with a molar excess of a dihalide of the formula: EQU Hal - L - Hal
wherein Hal represent a halogen atom and L is selected from --.sub.2 CH.sub.2 --O--.sub.2 CH.sub.2 --, --.sub.2 CH.sub.2 --O--.sub.2 CH.sub.2 --O--.sub.2 CH.sub.2 --, --(CH.sub.2)t--and --CH.sub.2 CHOHCH.sub.2 --where t is an integer from 2 to 6 and thereafter reacting the product so formed with a compound of the formula III ##STR5## wherein R.sub.1, R.sub.2, R.sub.3, and R.sub.4, are each individually selected from the group consisting of C.sub.1-3 hydroxyalkyl and hydroxy polyoxyalkylene and p, and q are each individually integers of from 1 to 6 and, if necessary, in order to ensure a total molar ratio of compounds of Formulae II and III to those of the formula Hal - L - Hal of 1:1, reacting the product with further compound of the formula Hal - L - Hal.
These products are stated to be of use as anti-static- aids in detergent formulations and as flocculating agents. Example 7 describes a clay compaction test using such block copolymers at low concentrations with Accugel F, a smectite-type clay at a pH of 5.0 5.9 in which it was found that at these pH's the block copolymer had a compacting effect on the clay.
U.S. Pat. No. 3,734,889 (Lipowski issued May 22, 1973) describes the use of a polymer obtained by condensing polyamines having one primary amino group and one tertiary amino group with a chain extender to produce products useful as flocculents, drainage aids and dry strength resins in paper manufacture, for example, to assist in removal of fillers and fines used in the paper making process.
U.S. Pat. No. 4,505,833 (Lipowski issued Mar. 19, 1985) describes the use of quaternized oligomers, including those obtained by reacting dimethyl amino propylamine with a dicarboxylic acid to prevent, inhibit or reduce swelling or migrating of clay particles including swelling clays such as smectites in a clayey geological formation. Results are reported of the effects at a pH of about 5.9.
U.S. Pat. No. 4,247,476 (Haase et.al. issued Jan. 27, 1981) describes a certain type of polymeric quaternary ammonium salts which are stated to be of use as dying and finishing agents in the textile industry and as dispersing agents and emulsifiers as anti-static anti microbial and flocculating agents and as precipitants.
Jacquet U.S. Pat. No. 4,517,174 describes cosmetic uses for a wide variety of polycationic polymers. Similar uses for certain bis(quaternary ammonium) derivatives are described in Zorayan's U.S. Pat. No. 4,612,188.
U.S. Pat. Nos. 4,536,305 (Borchadt et.al.) and 4,563,292 (Borchadt) describe the use of polymeric materials having side chains containing quaternary ammonium groups for use in treating formations containing smectite-type swelling clays to render them less swelling thereby facilitating the extraction of oil or gas from geological formulations in which such clays occur. This is effected by replacing ions present in the clay by potassium, calcium, ammonium and hydrogen ions that render the clays less swelling. The polycationic polymers are stated to be helpful in retaining replacement ions in place.
U.S. Pat. No. 4,532,052 (Weaver et.al.) describes several new treatment processes and compositions for practicing them. These processes substantially alter the fluid flow and surface characteristics of porous permeable particular formations, especially subterranean formations intersected by an oil well. The compositions of this invention also provide methods of increasing viscosity or gelling aqueous fluids, especially acids, which can be used to treat such earthen formations. A wide variety of polymers is described including branched organic polymers of a wide molecular weight range. The branches are preferably hydrophilic and the polymer contains bonding groups (e.g., ionic bonding groups) which serve to attract or repel a substrate, a particular formation, suspended solids, other polymers or segments, carrier fluid or a fluid to be treated.
U.S. Pat. No. 4,390,689 (Jacquet et.al. issued June 28, 1983) describes a variety of polycationic polymers that are said to be useful in the treatment of hair and skin and natural and synthetic fibers.
U.S. Pat. No. 4,695,402 (Finlayson et.al. issued Sept. 22, 1987) describes organophilic clay gellants prepared by a process wherein the smectite-type clay is subjected to shearing in order to break apart the agglomerates and/or the smectite-type clay and reacted with organic cation and, possibly organic anion, under dilute reaction conditions. The reaction product is recovered using gentle drying conditions. Depending in large part on its oomposition, the organophilic clay gellant may be used to thicken a variety of organic compositions. It is stated that in a preferred aspect, the organophilic clay gellant can be directly added to polyester compositions in order to efficiently and effectively increase the viscosity thereof or can be first formed into a pregel under low shear conditions to yield even higher efficiencies. The cationic materials employed include monomeric ammonium salts such as benzyl dimethyl hydrogenated tallow ammonium chloride. However, no suggestion is made of any use of polymeric cationic materials.
U.S. Pat. No. 3,594,212 (Ditsch issued Jul. 20, 1971) described the treatment of cotton fibrous material with an alkali metal or acid montmorillonite clay with a polyamine or polyquaternary ammonium compound to impart softness. It is stated that any montmorillonite clay can be used and any polyamine or polyquaternary ammonium compound that is water soluble. However, polyimines are preferred. Polymers of the type described in U.S. Pat. No. 3,594,212 are discussed in U.S. Pat. No. 4,141,691 (Antonetti et.al., issued Feb. 27, 1979). This indicates that such polymers may have a flocculating effect on clays.
U.S. Pat. No. 4,677,158 (Tso et.al.) describes the use of a high molecular weight polyethoxylated quaternary ammonium monomer compound to treat certain smectite clays to render them useful as thickeners for aqueous suspension such as latex paints.
U.S. Pat. Nos., 4,610,801 and 4,711,727 (Matthews et. al. issued Sept. 9, 1986 and Dec. 8, 1987 respectively) describe the slurrying of mineral particles possibly including a synthetic hectorite by using as flocculating agents various cationic and amphoteric polyelectrolytes such as polyamines. The slurries are stated to be useful in paper making and the treatment of sewage.
U.S. Pat. No. 4,365,030 (Oswald et.al. issued Dec. 21, 1982) describes higher dialkyl dimethyl ammonium clays of use as gellants of use for example in alkyd resin based coatings.
Another organophilic clay gellant is described in U.S. Pat. No. 4,412,018 (Finlayson et.al. issued Oct. 25, 1983). The product is a smectite type clay into which organic cations and anions have been intercalated. Among the possible cations mentioned are quaternary ammonium compounds.
Another gellant of this type is described in U.S. Pat. No. 4,434,076 (Mardis et.al. issued Feb. 28, 1984). In this case, a smectite-type clay is reacted with an organic cationic compound, such as a quaternary ammonium compound that possesses at least one .beta.,.alpha. unsaturated alkyl group or a hydroxyalkyl group of 2-6 carbon atoms, a long chain alkyl group and one or two relatively short chain alkyl groups.
U.S. Pat. No. 2,873,251 (Jones issued Feb. 10, 1959) describes the use of polyamines in drilling muds. Bentonite type clays may be pressed in the mud.
U.S. Pat. No. 2,807,910 (Erickson issued Oct. 1, 1957) describes the addition of polyquaternary ammonium compound as soil conditioners.
Organo-clay complexes are marketed under the tradename Bentone. Such complexes are made from simple monoquaternary ammonium salts, possessing one or more fatty alkyl groups on the quaternary nitrogen, and a smectite type clay. These complexes are lipophilic and are widely used to thicken oil-based systems such as alkyd paints, oil-based drilling muds and certain cosmetic formulations. They are generally formed under very specific conditions in aqueous media, then isolated, dried and marketed as solid products.